title: Photodecay dynamics of octaethylporphine in the condensed phase explored via resonance Raman spectroscopy and density functional theory calculation.
abstract: Resonance Raman spectra of free-base octaethylporphine (OEP) were obtained with 368.9 nm, 397.9 nm and 416.0 nm excitation wavelengths, and density functional calculations were done to help the elucidation of Soret (B(x) and B(y)-band) electronic transitions and the corresponding photo relaxation dynamics of OEP. The RRs indicate that the Franck-Condon region photo relaxation dynamics upon S(0)→S(8) electronic transition is predominantly along the totally symmetric C(m)C(α) stretch, the C(β)C(β) stretch, and simultaneously along the asymmetric δ(pyr deformation),γ(CH(2)) vibrational relaxation processes. The excited state structural dynamics of OEP determined from resonance Raman spectra show that the internal conversion between B(y) and B(x) electronic states occurs in tens of femtoseconds and the electronic relaxation dynamics were firstly interpreted with account of the time-dependent wave packet theory and Herzberg-Teller (vibronic coupling) contributions.
authors.affiliation: Department of Chemistry and State Key Laboratory of ATMMT(MOE), Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China.
authors.forename: Jiupeng
authors.initials: J
authors.lastname: Yin
authors.forename: Junmin
authors.initials: J
authors.lastname: Wan
authors.forename: Jun
authors.initials: J
authors.lastname: Xu
authors.forename: Huigang
authors.initials: H
authors.lastname: Wang
authors.forename: Xuming
authors.initials: X
authors.lastname: Zheng
mesh_terms: D000042:Absorption; D004583:Electrons; D008027:Light; D008752:Methylene Chloride / Q000737:chemistry; D008956:Models, Chemical; D044367:Phase Transition; D011166:Porphyrins / Q000737:chemistry* / Q000528:radiation effects*; D011789:Quantum Theory; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman / Q000379:methods*; D014732:Vibration
chemical_list: D011166:Porphyrins; D012996:Solutions; D012997:Solvents; D008752:Methylene Chloride